臺灣博碩士論文加值系統

製備出苯酚吲哚配位基L1(H2)-L4(H2)，並以正丁基鋰作為試劑在甲苯溶劑中進行反應，成功合成出鋰金屬錯合物36-39。合成出的一系列鋰金屬催化劑，以核磁共振光譜儀與元素分析儀進行鑑定，其中鋰金屬錯合物36透過X-ray單晶繞射儀確認晶體結構，是以四核四取代的三斜晶系結構存在。鋰金屬錯合物36-39於30°C下加入9-AnOH為反應條件，對左旋乳酸交酯進行開環聚合反應，這一系列鋰金屬催化劑都能夠在短時間內，展現出良好的催化活性。其中又以鋰金屬錯合物38的催化活性最為優秀，並且具備Living性質與Immortal性質，並以核磁共振儀與MALDI-TOF MS對開環聚合反應的聚合物進行尾端官能基的鑑定。

The lithium complexes 36-38 were synthesized from indolyl phenolate ligands L1(H2)-L4(H2) and n-Butyllithium in toluene. All complexes were characterized by NMR spectroscopy and elemental analysis. Additionally, the molecular structure of 36 was determined by X-ray single crystal diffractometer. The complexes 36-38 showed better catalytic activities for ring opening polymerization of L-LA in the presence of 9-AnOH at 30°C. Complex 38, revealed the highest catalytic activity, as well as the complex 38 exhibited both “ Living ” and “ Immortal ” properties. The end group analysis of polymer was characterized by 1H NMR and MALDI-TOF MS.

第一章、 緒論…………………………………………………………………........1
1-1 可生物分解之高分子聚合物…………………………………………..1
1-2 聚乳酸開環聚合的反應類型.......................3
1-3 金屬催化劑參與之反應機制.........................4
1-4 聚乳酸開環聚合反應副反應之交酯化現象及其鑑定方式.........6
1-5 金屬催化劑之設計與架構................................9
1-6 金屬催化劑在開環聚合反應中的應用........................10
1-6-1 早期工業金屬催化劑.......................................10
1-6-2 含有β-Diiminate(BDI)輔助配位基金屬催化劑...................10
1-6-3 NO-二牙亞胺苯酚基金屬催化劑...............................12
1-6-4 NNO-三牙亞胺苯酚基鹼金族金屬催化劑………………………...13
1-6-5 吡唑雙苯酚基鋰金屬催化劑...............................16
1-6-6 含有吲哚配位基之鋅金屬催化劑..............................17
1-7 研究方向……………………………………………………………...20
第二章、 實驗部分................................22
2-1 一般操作...............................22
2-2 溶劑處理...............................23
2-3 藥品處理...............................24
2-4 鑑定儀器...............................26
2-4-1核磁共振儀 (NMR，Nuclear Magnetic Resonance)...................26
2-4-2元素分析儀 (EA，Elemental Analysis)............................26
2-4-3 X-ray單晶繞射儀 (X-ray Single-Crystal Diffractometer).........27
2-4-4凝膠滲透層析儀 (GPC，Gel Permeation Chromatography)............27
2-4-5基質輔助雷射脫附游離高解析質譜儀(MALDI-TOF High Resolution Mass Spectrometer ) ..........28
2-5 養晶方式...........................................29
2-5-1單一溶劑......................................29
2-5-2兩種溶劑......................................29
2-6 吲哚配位基前驅物合成與鑑定..........................30
2-6-1 起始物7-Br-IndH..............................30
2-6-2 起始物7-Br-2-Ph-IndH..........................31
2-6-3 起始物2-Py-Br-IndH...........................32
2-6-4 起始物2-Ph-Br-IndH............................33
2-6-5 苯酚吲哚配位基L1(H2)...........................34
2-6-6 苯酚吲哚配位基L2(H2)...........................36
2-6-7 苯酚吲哚配位基L3(H2)...........................38
2-6-8 苯酚吲哚配位基L4(H2)...........................40
2-7 吲哚配位基鋰金屬催化劑合成與鑑定......................42
2-7-1 鋅金屬錯合物 36................................42
2-7-2 鋅金屬錯合物 37................................44
2-7-3 鋅金屬錯合物 38.................................46
2-7-4 鋅金屬錯合物 39.................................48
2-8 開環聚合催化反應之操作程序...........................50
第三章、 結果與討論............................................51
3-1 苯酚吲哚配位基前驅物之合成步驟與鑑定.......................................51
3-2 苯酚吲哚配位基鋰金屬錯合物之合成步驟與鑑定...........................53
3-3 苯酚吲哚配位基鋰金屬錯合物之晶體結構與解析...........................55
3-3-1鋅金屬錯合物 36之晶體結構與解析................................55
3-4 左旋乳酸交酯開環聚合反應.........................................57
3-4-1 左旋乳酸交酯開環聚合反應之條件優選...........................57
3-4-2 左旋乳酸交酯開環聚合反應之催化劑優選.............................58
3-4-3 錯合物38對Living性質以及Immortal性質之探討......................59
3-4-4 PLA聚合物尾端鑑定以及反應機制推測...............................61
第四章、 結論.........................................................63
參考文獻............................................................64
附錄................................................................66

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